Ice colors



Patented Dec. .15, 1936 ICE COLORS Frithjoi Zwilgmeyer, Wilmington,Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, DeL, acorporation of Delaware No Drawing. Application July 18, 1935,

- Serial No. 31,999

22 Claims.

This invention relates to azo colors and to methods of manufacturingthem. The invention also relates to new compositionsof matter, to newchemical compounds, and to processes of preparing them.

The azo dyes are a well-defined group containing the chromophor N=N--.The chromogen of azo dyestuffs comprises two aryl radicals with thechromophor between them. The monoazo dyes are generally prepared byjoining two components of which the first, an amine, is called the azocomponent, and the second, usually a phenol, an amine, or an activemethylene compound, is called the coupling component. In coupling thecomponents, the azo component is diazotized in a manner which will beunderstood by persons skilled in the art, and is reacted with the secondkyl, aralkoxy, halogen, nitro, acylamino, trifluoromethyl, 'carboxamido,sulfonamido, and the sulfonic-acid and carboxylic-acid groups. The twolast named have a solubilizing effect on the dyestuff and will not beused where a color insoluble in water is desired.

The prior art azo dyes are applied to fabrics, or to other materials tobe dyed, in three general ways: (a) The dyestuff is dissolved ordispersed in a suitable bath and the material is dipped in the bath. Tobe used in this manner the completed dyestuff must be substantive to thematerial which is to be dyed. (b) A substantive coupling component isdirectly afiixed to the fabric, which is then treated with thediazotized component, completing the dye on the material. (0) Asubstantive azo component is directly affixed to the fabric which,treated with the cou-- pling component, completes the dye on thematerial. In an application filed September 20, 1934 in the names ofMiles A. Dahlen et al, Serial No. 744,786, a material is dyed withsuperior results through the intermediation of a new process with colorswhich are not themselves substantive and whose components are notsubstantive. This invention is to a considerable extent a development ofthe invention disclosed in that application.

It is an object of this invention to prepare su-- perior azo colors.Another object of the invention is to dye materials in colors havingsuperior qualities by commercially and technically satis-v factorymethods. Another object of the invention is to produce new dyestuffs.Yet another object of the invention is to produce new compositions ofmatter and processes of preparing them. Still, other objects of theinvention will be in part hereinafter disclosed and in part apparent topersons skilled in the art.

The objects of the invention are accomplished,

generally speaking, by the new dyestuffs and processes of using themwhich are more fully hereinafter disclosed. More specifically theobjects of the invention are accomplished by coupling a diazotizedprimary arylamine to a furo-acetyl- 15 arylamide. It is within the scopeof the preferred form of the invention to prepare these new compoundsfrom mono amines or diamines of the benzene or naphthalene series andfrom furoacetyl-arylamides of the monoor diamine and 20 benzene ornaphthalene series, and to make them in the form of pigments, aswater-insoluble dye stuifs, and in a less preferred form as watersolublecolors.

In the preferred form of the invention the dye- 25 ing of a material,for instance the dyeing of cotton cloth, will be accomplished byimpregnating the cloth with an alkaline paste containing a stabilized,diazotized arylamine and a furo-acetylarylamide, and by exposing theimpregnated cloth 30 for short time to the action of acid vapors, forinstance acetic acid vapors, at elevated temperature.

The following description is of the preferred form of the invention, andthe disclosure therein should not be interpreted as limiting. 35

There may be used as the diazo component any primary arylamine. Thesearylamines are nauxochrome substituted in some cases and in other casesare without substituents other than the amino group. Generally speaking,the arylamines I having auxochrome-substituted nuclei are superior.Among the classes of amines whose members are suitable are the benzenes,naphthalene, diphenyl, anthracene, fluorene, carbazole, azobenzene,stilbene, azoxy-benzene, diphenyl amine, diphenyl ether, diphenyl oxide,diphenyl-sulfone, phenanthrene, and pyrene series. It is understood thatthis list is exemplary, not limitative. The low cost, excellence, andavailability of the aniline and naphthylamine series of arylamines 5lead to their use in a majority of cases. Exemplary of these classes andof the use of auxochrome substituents are the following compounds:Z-methoxy-naphthylamine; 2-methoxy-ani1ine; 2-phenoxy-aniline;2-ethoxy-aniline; 2-chlor-5- methyl-aniline; Z-methyl-aniline;2-methoxy-5- methyl-aniline; aniline; 2 :S-dimethoxy-aniline; 2:5-diethoxy-anline; 2 5-dimethoxy-4-chlor-aniline; 5-brom-2-methoxy-aniline; 3-iodo-6-methoxy-ani1ine; 3- iodo-fi-ethoxy-aniline;3-methyl-4-chlor-aniline; 3-brom-6-ethoxy-aniline;3-chlor-6-ethoxy-aniline; 3 ethoxy aniline; 3 phenoxy aniline; 3'-methoxy-aniline; 3-brom-6-phenoxy-aniline; 3- iodo-6-phenoxy-aniline;3-brom 6 methyl-aniline; 3-chlor-6-methyl-aniline; 3-methyl-aniline;3-brom-5-methyl-aniline; 3 chlor 6 phenoxyaniline; 2fi-dimethyli-chlor-aniline; 4-ethylaniline; 4 benzo triiluor aniline; 4chlor 2- methoxy-aniline; 4-brom-2-methoxy-aniline; 4-brom-2-ethoxy-aniline; 4 iodo-2 methoxy-aniline; 4-methoxy-aniline;4-chlor-2-ethoxy-aniline; 4 phenoxy aniline; 4 ethoxy aniline; 4-brom-2-phenoxy-aniline; 4-methoxy-2-chlor-aniline;4-chlor-2-methyl-aniline 4-methyl-3-bromaniline;4-brom-3-methyl-aniline; 4-methyl-3- chlor-aniline; 4-methyl-aniline;4-chlor-2 5-dimethyl-aniline; 4-chlor 2 phenoxy aniline; 4-methoxy-3-chlor-aniline; 4-phenoxy-2-chlor-aniline;4-chlcr-2:5-diethoxy-aniline; 3-ethoxy-aniline; 8-methoxy-ani1ine;3-methyl-aniline; 3- chlor-2-methy1-aniline; 3-chlor-2-methoxy-aniline;2 ethoxy aniline; 2 methoxy aniline; 2- methyl aniline; alphanaphthylamine; betanaphthylamine.

In the practice of the preferred form of the invention the azocomponent, diazotized, is coupled with a stabilizing agent: Forinstance, it is joined by the azo group to the nitrogen group ofpiperidine carboxylic acid. After stabilization this component can bemixed with the coupling component without reaction provided the mixtureis alkaline. The presence of an acid medium would break up thestabilized azo component, which would immediately react with thecoupling component to form the complete color.

A great variety of compounds are useful as coupling components. Thiscoupling component is a furoyl-acetyl-arylidehaving an aromatic nucleus.that may or may not have an auxochrome substituent. Thefuroyl-acetyl-arylamide may have an aryl group from any of the knownclasses, exemplary of which is the list hereinabove given in connectionwith the diazo components. Exemplary of particular classes, and of theuse of auxochrome substituents in the aryl nucleus thereof are thefollowing: furoyl-acetyl-4-chloro-aniline;furoyl-acetyl-4-methyl-aniline; furoyl-acetyl-4-phenetidine;furoyl-acetyl-2 :5-diethoxy-aniline; furoyl-acetyl2-methyl 5 chloroaniline;

furoyl-acetyl-Z methoxy naphthyl amine; die

furoyl acetyl tolidine sulfone; furoyl acetyl- 25-dimethyl-4-chloro-aniline; furoyl-acetyl-2 :5-diethoxy-4-chloro-aniline; furoyl-acetyl-Z-methoxy-aniline; furoylacetyl 2:5 dimethoxy-aniline; furoyl-acetyl-2-methoxy-5-chloro-aniline;furoyl-acetyl-para-anisidine; furoyl-acetyl tolidine-azone; and thosewhich are elsewhere herein disclosed.

Methods of preparing these new compositions of matter are disclosed inmy copending application filed of even date herewith. I

In the form of the invention which involves the dyeing of a cloth by theso-called process of printing, the azo component, diazotized andstabilized 2-methoxy-4.-chlor 5 methylin the well-known manner, is mixedin a basic paste with the second component, and the paste is applied toan etched or printing'ro1le r which impregnates the fabric by contact.The fabric may then be placed in a closed container to be subjected fora few seconds at elevated temperature to the action of the fumes 01' anacid, usually in the presence of water vapor. The acid used mayconveniently be acetic acid. The acid neutralizes the basicity of thepaste, the piperidineal'pha-carboxylic-acid complex is broken up, thefirst component is freed, and reacts with the coupling component.

The colors which are formed by this invention fall generally within thename aryl-azo-furoylacetyl arylamides. This term includes compoundshaving the following formulae:

in which Aryl represents an aryl nucleus, and which are made by couplinga diazotized arylamine to a furoyl-acetyl-arylamide;

in which Aryl represents an aryl nucleus, R is an arylene diaminenucleus, and which are made by coupling a diazotized arylamine to afuroylacetyl-arylene-diamine; and

in which Aryl is an aryl nucleus as above described, and R is atetrazotized arylene-diamine. These compounds are made by coupling atetrazotized .arylene-diamine to a furo-acetyl-arylamide.

The following examples, in which parts are by weight, illustrate but donot limit the invention.

Example I A printing paste was prepared from the following ingredients:

. Parts Diazo-imino compound prepared by .the

reaction of diazotized 4-chlor-2-aminotoluene with the sodium salt ofpiperidine-alpha-carboxylic-acid in alkaline HC=CH I The dyeingspossessed a high degree of fastness to light, laundering and bleachingagents.

Example II A printing paste was prepared from the following ingredients:

Parts Diazo-imino compound prepared by the reaction between diazotized4-chlor-2- amino-anisole and the sodium salt ofpiperidine-alpha-carboxylic-acid in alkaline solution 3.2

4-ethoxy-furoyl-acetanilide 2.8 Ethylene-glycol-mono-ethyl-ether 6.0 A26% solution of sodium hydroxide 2.0

Starch: gum tragacanth thickener 50.0 Water at 140 F--- Cotton goodswereprinted with the above paste from an engraved copper 'roll, and thenweredried. The cloth was exposed for 1 and minutes to the vapors of aboiling 5% solution of acetic acid. It was then rinsed, soaped for 1minute at 160 F. in a 1% soap solution, rinsed again and dried. Thecloth was dyeda bright reddish yellow by the dye'stuff represented bythe formula:

Cl i

The dyeings possessed a satisfactory degree of fastness to light,laundering and bleaching agents.

Exainple III The 'color components in the printing paste described inExample I were replaced by these:

. I Parts Diazo-imino compounds prepared by the reaction of diazotized6-chlor-2-aminotoluene with the sodium salt of piperidine-alphacarboxylic acid in alkaline solution 3.2 And 4-ethoxy-furoy1-acetanilidelowing The paste was applied on cotton goods and developed in the mannerdescribed in the previous examples. The goods were dyed a reddish yellowby the dyestuff represented by the formula:

The dyeings possessed a satisfactory degree of fastness to light,laundering and bleaching agents.

Example I V A printing paste was prepared from the followingingredients:

' A Parts Diazo-imino compound prepared by the reaction betweendiazotized 6-chlor-2- amino-toluene and the sodium salt ofpiperidine-alpha carboxylic acid in' alkaline solution 3.1 25'-'dimethyl-4-chlor-furoyl-acetanilide' 2.9Ethylene-glycol-mono-ethyl-ether 6.0 A 26% solution of sodium hydroxide2.0 Starch: gum tragacanth thickener 50.0 Water at 140 F -1 36.0

Total ....1 100.0

' Cotton goods were printed with this paste from an engraved copperroll, and dried. The cloth then was exposed for 1 and A, minutes to thevapors ofa boiling 5% solution of acetic acid; it was then'rinsed,soaped for 1 minute at 160 F. in 1% soap solution, rinsed and dried. Thegoods were dyed a reddish yellow'by a dyestufi represented by theformula:

/HC=CH O C==CH Cl CH: I CH1 1 v The dyeings possessed a satisfactorydegree of fastness to light, laundering and bleaching agents.

Example V The color components in the printing paste described. inExample I were replaced by the fol:

Parts -Diazo-imino compound prepared by the reaction between diazotized6-chlor-2-amino-toluene and piper-idine-alpha-carbox ylic acid 3.1

'-2 methyl-5-chlor-furoyl-acetanilide 2.9

The paste was prepared, applied and developed on the fiber in the mannerdescribed in the pre- /HC=CH Example XII A printing paste was preparedfrom the fol- C=CH lowing ingredients: 00 Parts Water-solublediazo-imino compound prepared by the action of diazotized 4- Hchloro-Z-amino-toluene on piperidine- C1 CH3 alpha-carboxylic acid 3.3The dyeings possessed a' satisfactory degree ofBis-(furoyl-acetyl)-tolidine-sulfone 2.7 fastness to light, launderingand bleaching Ethylene-glycol-mono-ethyl-ether 6.0 agents. A 26%solution of sodium-hydroxide 2.0 I The following color components alsoyield yel- Starch: gum tragacanth thickener 50.0 low dyestuffs ofcommercial interest when de- Water at 140F 36.0

veloped on cotton goods in the manner previously described: Total 100.0

fi 1e Cou lin om nent Diazocom' F min] t th t i! BN3. 1) go P0 ponent 0B represen 111g 6 YES 11 VI 4-methyl-furoyl-acetanilide. 4-chlor-2-HC=CH aminotoluene O VII. 4-methyl-furoyl-aeetanilide. 4-chlo ro-2- H(1:0 11

aminoanisole. 0\

0:011 OCH: I

VIII... 2:5- diethoxy luroyl acet 4-chloro-2- HC=CH anllide.aminoanisole. 0

0:011 CH; 4 OCIHI 1 N=N(JCONH IX 2:5 diethoxy luroyl acet 4-chloro-2-HC=CH anilide. aminoanisole. O

C=CH OCH: OCSEI l l 0 l N=N(|JCONH E 1 cm. X 2:5-diethoxy-4chlor-1uroyl- 4-chloro-2- I HC= H acetanilide. aminoanisole.

C: H OCH: 001m H 01 C111; v

XI 2:5-diethoxy-4-chloro-iur0yl- 4-chloro -2- HC=CH I acetanilide.aminotoluene. '0

. C=CH CH; I 001K;

. n Cl OCQHB vious examples. The fiber was dyed a bright reddish yellowby the dyestufi represented by the formula:

The following examples illustrate the phase of the invention in which adiazotizedarylamine is coupled to a furoyl-acetyl-arylene-diamide:

Cotton goods were printed with the above paste, and the color developedas in Example I. The pattern appeared as abright yellow represented bythe formula:

| I HCCH CONH- -NHco ..t that. l N N CH-C 0- agent, such as sodiumacetate, sodium bicarbonate, and sodium carbonate, or the like. Thecolors formed are insoluble in water, and are separated by precipitationand filtration; Such u N N l l 01 Cl fi g Coupling component 3522,Formula representing the dyestufl XIII Bis (furoyl acetyl).- 4 chlo ro(3H tolidine. I 2-am1notoluene. CH;

1 N 0 I I G1 -I N N 01 m fi-COCHCONH-OQ-NHCOCHCO-(fl) on H C-CH I IHC--C H CHz CH:

(Yellow) XIV. Bis (furoyl acetyl) 4 chloro 0 1:5 diamino-naphtha-2-am1no O CH; lene. anisole. EH) (?-$0 l HC---OH CHN=N to i,

| O CH: l O 330 0-0 0 l I ll 01 (Yellow) XV 2:5:4-trimethoxy -4 ami-Bisiuroyl- Red.

noazo-benzene. acet y l tolid in esulfone. XVI Furoyl-aeetyl-para-anisi-Dianisidine Orange.

ne. XVII. Furoyl-aeetyl-4-chloro-2- Dianisldine Reddish-yellow.arnino-anisole.

It also will be apparent that the colors may be.

produced in the form of insoluble pigments by the procedureswellrecognized in the art. For instance, if it is desired'to prepare thecolor apart from a material, the preparation can'be carried out bydissolving or suspending the coupling component in an aqueous medium,adding the diazo solution in the presence of an acid binding pigmentsare of value e. g. in the coloring of rubber, in printing inks, and inplastics.

The foregoing examples illustrate the use of the colors as'self-shades.However, they also may be used in mixtures,toproduceawide range ofshades. For example, the product of Example No. I may be mixed invarious ratios with the mixture of the water-soluble diazo-iminoderivative of 4- chloro-2-amino-toluene and the orthophenetidide of2:S-hydroxy-naphthoic-acid. From such a mixture, brilliant orange shadesof excellent fastness may be produced by the usual processes of dyeingand printing. Likewise, the colors may be produced in combinations withreds and blues to yield a wide range of browns and blacks.

'Among the stabilizing agents useful in stabilizing the azo component Iname, as examples but not as a limitation: sarcosine, ethyl-taurine,proline, 4-sulfo-2-amino-benzoic acid, methylglucamine. The use ofstabilizers such as these for the preparation of water-soluble diazoamino compounds is well-known in the art.

By this invention there may be produced dyes which are of outstandingfastness, some of which appear to be equal to vat dyes in this regard,and which, being much less expensive, are of great commercial value.These dyes constitute a great advance over the insoluble yellow azo dyesknown to the prior art, being far more permanent. Other advantages ofthe invention reside in the extension of the inventive idea of the abovidentified Dahlen et al. application and in the -processes thereof.

As many apparently widely diilerent embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that I do not limit myself to the specific embodimentsthereof except as defined in the appended claims.

I claim:

1. The method of dyeing which comprises impregnating cotton goods with apaste containing 2.3 parts ofchlor-methyl-benzene-azo-alphacarboxy-piperidine, 2.8 parts of4-ethoxy-furoylacetanilide, 6 parts ethylene-glycol-mono-ethylether, 2parts 26% sodium hydroxide water solution, 50 parts starch gumtragacanth thickener. and 36 parts water, drying the goods, exposing itfor one and one-quarter minutes to the vapors of 5% acetic acid watersolution, rinsing, soaping for one minute at 150 F. in a 1% soap watersolution, rinsing and drying, the goods being dyed yellow.

2. The method of dyeing which comprises impregnating a material with analkaline paste containing chloro methylbenzene-azo-alphacarboxy-piperidine,4-ethoxy-furoyl-acetanilideethylene-glycol-mono-ethyl-ether, and starchgum tragacanth thickener and water, drying the material exposing it atelevated temperature to acetic acid vapors, rinsing, soaping, rinsing,and drying.

3. The method of dyeing which comprises impregnating a material with analkaline paste containing chloro-methyl-benzene-azo-carboxy-piperidine,4-ethoxy-furoyl-acetanilide, ethyleneglycol-mono-ethyl-ether, athickener, and water, and acidifying, washing, and drying theimpregnated material.

4. The process which comprises incorporating in an alkaline mediumroughly equivalent quantities ofchloro-methyl-benzene-azo-carboxy-piperidine and4-ethoxy-furoyl-acetanilide, acidifying the medium, and removing thecolored product therefrom.

5. The process which comprises coupling a diazotized arylamine of theclass consisting of the benzene, naphthalene, diphenyl, anthracene,carbazole, azo-benzene, azoxy-benzene, diphenylamine, diphenyl-ether,phenanthrene, and pyrene series to a furoyl-acetyl arylamide one of agroup consisting of benzene, naphthalene, diphenyl, anthracene,carbazole, azo-benzene, azoxy benzene, diphenylamine, diphenyl-ether,phenanthrene, and pyrene, the aryl nuclei of which may have assubstituents members from the group consisting of alkyl, alkoxy, aryl,aryloxy, aralkyl, aralkoxy, halogen, nitro, acylamino, triiluoromethyl,carboxamido, and sulfoamido.

6. The method of making a dyestufi of yellow cast which comprisescoupling a diazotized primary arylamine to a furoyl-acetyl-arylamide.

'7. Chloro-methybbenzene-azo furoyl acetyl phenetidine.

8. A dye being a diazotized primary arylamine coupled to afuroyl-acetyl-arylamide.

9. A dye being the product of coupling a (hazetized primary arylamine toa furoyl-acetyl-arylene-diamide.

10. A dye being the product of coupling a tetrazotized arylene diamineto a furoyl-acetyl-aryl- 6 amide.

11. A product represented by the formula:

in which the aryl nuclei has as suhtituents one or more of the groupalkyl, alkoxy, aryl, aryloxy. aralkyl, aralkoxy, halogen, nitro,acylamino, trifluoro-methyl, carboxamido, hydrogen and su1-.

in which R is the nucleus of an arylen'e diamine. 80

13. The product represented by the formula:

in which R is the nucleus of a tetrazotized arylene 40 diamine.

14. The product represented by the formula:

15. A fiber dyed with the dyestufi of claim 11.

16. A fiber dyed with the dyestuif of claim 12.

17. A fiber dyed with the dyestuif of claim 13. I 18. A fiber dyed withthe dyestufi of claim 14.

19. The process which comprises incorporating in an alkaline medium adiazotized arylamine of the class consisting of the benzene,naphthalene, diphenyl, anthracene, carbazolc, azo-benzene,azoxy-benzene, diphenylamine, diphenyl-ether, phenanthrene, and pyreneseries, and a furoylacetyl-arylamide, and acidifying the medium.

20. The process which comprises incorporating in an alkaline mediumdiazotized chloramino-toluene and furoyl-acetyl-phenetidine, andacidifying the medium.

21. The process which comprises incorporating in an alkaline medium adiazotized primary aryl- "amine and a furoyl-acetyl-arylamide, andacidi- FRITHJOII ZWILGMBYIR.

CERTIFICATE OF CORRECTION.

Patent No. 2,064,332. December 15, 1956.

FRITHJOF ZWILGMEYER.

It is hereby certified that error appears in the printed specificationof the above numbered 'patent requiring correction as follows; Page 6,second column, line 17 claim 11, after the word "group" insertconsistingof; and that the said Letters Patent "should be read with thiscorrection therein that the same may conform to the record of the casein the Patent Office. I

Signed and sealed this 30th day of March, A. D. 1937.

Henry Van A rsdale ISeal) Acting Commissioner of Patents.

